Method of making beryllium and light alloys thereof



Dec. 5, 1933. l.. BuRGEss 1,937,509

METHOD OF MAKIG BERYLLIUM AND LIGHTALLOYS 4TI'IEREIOF Filed Jan; 16, 1932 iNvENToR m e NYM UNITED STATES PATENT. oFl-lcE METHOD F MAKING BERYLLIUM.l AND LIGHT ALLOYS THEREOF Louis'Burgess, New York, N. Y.

Application January 16, 1932. Serial No. 587,126

-9 Claims. (Cl. 2104-19) The invention will be fully understood from compound, and in which electrolyte the beryl the following description read in conjunction lium compound has a lower voltage of dissociawith the drawing, in which,. tion than the other constituents present.' unless Fig. 1 is a` vertical section through apparatus of course the process is operated to simultane- 5 in which my,y invention may be carried into efously produce an alloy of other elements than go fect. J I beryllium. Preferably, however, the beryllium Fig. 2 is ay vertical section of apparatus in compound present in the electrolyte is the niost which a further embodiment; of my invention .easilyh dissociable compound upon electrolysis.vl may be carried into eiect. Within the limits of :temperature at which ,the

1g Fig. 3'is a cross-section through a further form alloy consisting of lberyllium and copper is fluid, 65'

` of apparatus in which another embodiment of the electrolyte must consist essentially of fluorthe invention may be carried out. ides. It may consist predominantly of another Referring specically to Fig. 1, the apparafluoride or iluoridesof yhigher dissociation tus comprises the casing or shell 1 which may potential than beryllium vuoricle, containing be of iron or Vsteel and which contains the lining in solution a few percent of berylliumA fluoride 70 l or layer 2 which operates as electrical and therand/or beryllium oxide.v Preferably.. however,

mal insulation between the fluid contents of the the electrolyte 6 contains a substantial proporapparatus and the shell. The lining 2 may either tion of beryllium fluoride, and to impart the. be built up of preformed blocks of suitable re-v maximum fluidity and conductivity at least onev fractory material, or may be formed in situ by fluoride with an element more electropositive 75 lling the shell 1 with fluid electrolyte and perthan lberyllium and which therefore formsa-flumitting the same to solidify in part adjacent the oride of higher dissociation potential should be shell 1 thereby forming the lining 2. 3 desigpresent. The fluorides of the-alkali metal and nates a bridge wall `which may also be formed of alkaline earth metals conform to this description.

5 suitable refractory material, but is preferably In this case, a few percent of beryllium oxide may 80 formed in situ through freezing electrolyte about be present dissolved in the uoride electrolyte the pipes 4 which are connected in series so that 10 indicates an anode which may bev of any suit'- a suitable cooling fluid may be circulated through able type, but preferably consists of a rod of. the same. The layer 5 may, generally speaking, carbon or graphitized carbon carried by the be composed of an alloy of beryllium with heaviholder' 1l. It will of course be understood that Q5 er metals which are less electropositive than a number of such rods are employed in parallel beryllium. A number of binary and ternary alsufficient to carry the requisite amperage into loys of this sort may be formed which will operi' the apparatus. In carrying out the operatim, ate in the process. The alloylng metals should currentA is applied to the anode 10 whereby the I,35 be substantially heavier than beryllium, less elecelectrolyte 6` is electrolyzed in series with the 90 tropositive than berylliumin relationship to the alloy layer 5 as cathode, thereby dissociatingjhe electrolyte employed, and the :alloy formed beryllium compound .in solution inthev electro-,I should be freely iiuid at the temperature of eleclyte 6 and,liberating beryllium at the surface 12 trolysis. 'Ihe alloy must exist as a single homo-A of the alloy 5. The. alloyswill undergo,consider-v 40 geneous liquid phase. lWhile silver may be emable flow during .elecfrOlySiS Adill? D'IDODSUY'O 95 ployed, I prefer to form the layer 5 of an alloy Athe electrical eld to which it i3 Sl-Ilected. and u consisting predominantly of beryllium and copthe beryllium liberated at the surface 12 will per, or of beryllium and copperbontaining a few therefore be incorporated with the main body of percent of silicon, which latter agent will operthe alloy. In order to produce the elemental ate within certain rang'es of concentration to deberyllium, either per se or inthe -form of a light 1o@ press the freezing point and impart greater fluidalloy Oiberyllium, the 8.1105' layer 5 1S Electroity. Alternatively, or in addition to the silicon, lyzed as; anode through a. suitable electrolyte inV there may be added afew percent of other metals series with a suitable cathode. This may, generless electropositive than beryllium which havea ally speaking, be done either simultaneously with low melting point and are normally liquid at the or in succession to the ostepshereinbefore de- 105 'temperature of electrolysis. In any event, the scribed.

alloy so-formed'should have a specic gravityin In the apparatus illustrated in Figs. 1 and 2, excess of `3 at the temperature of electrolysis.A the second ,stage electrolysis with the copper, The layer 6 indicates generally a suitable elecberyllium alloy as anode is carried simultaneously n trolyte containing -an electrolyzable beryllium with the first stageelectrolysis hereinbeiore de- 110y I scribed. In this case, the uid electrolyte 13 floats upon a. part of the alloy layer 5. The cathode 14 may be of any suitable type and preferably consists of a rod of carbon or graphitized carbon carried by a suitable holder 15. It will of course be understood that while one rod is diagrammatically shown for purposes of illustration, a number of such rods will be employed in parallel, de-

pending upon the total amperage to be carried through the electrolyte. When making pure beryllium unalloyed with other metals, the material will plate out in solid phase as a body 16 of U metal adhering to the lower end of the cathode A ture of electrolysis may range from a temperature in the electrolyte approaching the melting point of beryllium down to the lowest temperature at which the alloy layer 5 and the electrolyte will be freely iluid. When operating with an alloy layer 5 consisting almost entirely of `copper and beryllium, temperatures of from 950 to 1250 are preferred. A temperature of from 1100 to 1200 is prefered. In this case the alloy layer, 5 preferably contains from 4 to 12% by weight of beryllium. 'Ihe addition of other metals to the alloy layer 5 which depress the freezing point will materially extend the range of temperatures within which tlie operation may be eiiiciently ca rried out, and will also render it possible to o erate with higher percentages of beryllium. ere the alloy layer 5 consists entirely of copperrand beryllium, the melting point starts to rise sharply as the beryllium content is increased above 10%. The applied .voltage will be suflicient to carry the necessary amperage through the furnace, and the twoiactors of amperage and voltage will be so correlated as to maintain the de-` `corresponding Vparts have been identined by corresponding numerals. 'I'he apparatus shown in Fig. 2 is. however, designed to eliminate the -necessity `for removing solid beryllium from the extremity' of the cathode 14 and to permit fthe material to be handled in liquid phase. In this case the rod 14 contacts with a layer 20 of light metal or alloy iloating upon the electrolyte 13. This may for example be a layer of beryllium aluminum alloy; or may alternatively at the start of the operation be a layer of pure aluminum. In either event, the `electrolyte must .be so compounded as to oat the layer 20 which is in this case the true cathode throughout the entire range of concentrations. In* general, the layer- 20 will become lighter during electrolysis owing. to in crease in its beryllium content, and the electrolyte should be compounded to support the layer 20 in its condition of' maximum density. In this case, vparticular attention must be paid to the l composition of the electrolyte, and fluorides of the alkali metal and/or alkaline earth metals be present in suilicient amounts to make the electrolyte more dense than the layer. 20 throughout the entire operation. This may be eiected by the use of barium fluoride and potassium uoride in amounts sufficient to impart the requisite density. An electrolyte in roughly the following proportions is recommended:

' Percent Berylliimi fluoride 7 20-25 Barium fluoride 35-40 Potassium fluoride s 35-40 With the apparatus shown in Fig. 2, the operation is continued until the layer 20 has attained the desired concentration of beryllium. The concentration of beryllium in the layer 20 must not be permitted to reach such a point as to cause solidication or thickening of the same. The danger point may', however, be readily determined by comparing the temperature of electrolysis with tables showing the melting points of beryllium aluminum'alloys.- When the predetermined concentration "of `beryllium has been reached in the layer 20, it may betapped from thecell into any suitable receivingvessel through the tapping duct 21 which is normally closed by means of the plug 22. When this has been done, the layer 20 is replenished either with pure aluminum, or an alloy of beryllium and aluminum containing less than the desired beryllium content and operations resumed.

During the operation, uorine generated in the iirst stage of electrolysis at the lower extremity of the anode 10'will pass out of the apparatus without contact with the beryllium or aluminum alloy undergoing formation. This eliminates complications due to thepresence of fluorine and sov beryllium inthe same space as it occurs in the ordinary and prior art method of generating beryllium. The elimination of the iluorine at the lower end of the anode 10, moreover, renders it possible to iloat the cathode layer 20 on the electrolyte 13. While the operation may be carried out withoutreplenishment oi' the beryllium compound in the electrolyte 6, it is preferably carried out with the intermittent or continuous replenishment of the beryllium compound in uniform composition of the electrolyte 6 throughthe same so as to maintain a. substantialout the operation. The electrolyte 13 does not normally undergo substantial change, inasmuch as beryllium passes into the same from the alloy 5 in amounts equal to that liberated at the cathode'14. The composition of the alloy layer 5 will not undergo substantial change in operation as the amount of beryllium abstracted from this layer is substantially balanced by that introduced.

The operation may be eifectively carried out in the relatively simple apparatus shown in Fig. 3. This comprises the shell 30 which carries the carbon lining 31 adjacent the-interior lower portion ofthe shell. This may consist of a carbon lining tamped into position and suitably bonded, or may alternatively consist of preformed carbon blocks laid and cemented in position. The block type has been illustrated in the iigure. Electrical contact withl the carbon lining or pit may be made in any suitable manner. formillustrated, the block 32 adjacent ,the iioor of the shell 30 is formed, with a machined cylindrical butt 33 which ilts snugly into the annular water' cooled sleeve 34'. This is sealed to the Vshell 30 and carries the end closure 35 to which the bus-bar 36 is connected. The upper part of the shell carries a thermalikand electrically insulating lining 40, preferably formed in situ by "ist,

freezing electrolyte on the walls of ,the shell. The electrode 41 which may consist of carbon or g'raphitized carbon is carried by the holder 42 and several such electrodes are employed in parallel to carry therequisite amperage. 'I'he pit 31' carries the alloy 5 hereinbefore described, and the electrolyte-43 is provided floating upon the surface of the fluid alloy 5. In operating this apparatus, electrolysis is carried out for a period with the electrode 41 as anode and the alloy as cathode. During this period, the concentration of beryllium in the layer 5 is continuously increasing. Before the concentration of Iberyllium in the layer 5 reaches such'a point as to cause undue loss of fluidity or freezing, the operation is/reversed, making the layer 5 anode and the electrode 41 cathode, so that the beryllium is plated out on the lower end of the electrode 4l. As the layer 5 becomes impoverished in beryllium, the operation is discontinued and the beryllium removed from the lower end of the electrode 41. The electrolyte does not change in composition duringthe second stage of operation and is preferably held constant by suitable replenishments during the flrst stage.

In the preferred method of operating this apparatus, the electrolyte is compounded as hereinbefore described to support a cathode layer of aluminum or of beryllium aluminum alloy consisting principally of aluminum. In this 'case, electrolysis is started with the electrode 41 as anode and the alloy layer 5 as cathode and carried out preferably'with suitable replenishments of the dissociated beryllium compound until the layer 5 has become enriched in beryllium content. The operation is then temporarily discontinued. The electrode 41 is raised slightly and a layer of molten aluminum or aluminum beryllium alloy is gently introduced; so that it oats on the surface of the electrolyte 43. The electrode 41 is then adjusted-to contact with the fluid metal introduced, which latter then becomes the true cathode. Electrolysis is then continued with the alloy layer 5 as anode and the introduced light metal as cathode untilthe alloy 5 has become impoverished in beryllium, whereupon the light metal which has now become correspondlngly enriched in beryllium is tapped into a suitable receiving vessel through the duct 44 which is normally closed by the plug 45. l y

The foregoing description is for purposes of illustration, and it is therefore my intention that the invention be limited only by the appended claims or their equivalents in which I haveendeavored to claim broadly all inherent novelty.

I claim:

1. Process of making beryllium, which comprises maintaining a fluid alloy of beryllium and ametal or metals relatively more Vdense than beryllium and less electropositive than beryllium in relation to iluorine, maintaining floating on .at least a part of the said alloy a fluid electrolyte containing a metallic fluoride or fluorides of higher dissociation potential than beryllium fluoride,

.and containing a compound selected from the lected from the group consisting of beryllium oxide and beryllium fluoride, andelectrolyzing said last mentioned electrolyte in series with said fluid alloy as anode and in series with a suitable cathode, thereby depositing beryllium at the said last mentioned cathode.

2. Process of` making beryllium, which comprises maintaininga fluid alloy consisting predominantly of beryllium and copper, maintaining floating on at least a part of said fluid alloy a fluid electrolyte containing a metallic fluoride or fluorides of higher dissociation potential than beryllium fluoride and containing a compound selected from the lgroup consisting of beryllium fluoride and beryllium oxide, electrolyzing said electrolyte in series with said alloy as cathode and in series with a suitable anode, thereby dissociating said'beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in said fluid alloy, maintaining floating on at least a part ofthe .said fluid alloy an electrolyte containing a metallic fluoride or fluorides of higher dissociation potention than beryllium fluoride and containing a compound selected from the group consisting of beryllium fluoride and beryllium oxide, and electrolyzing said last mentioned electrolyte in series with said beryllium copper alloy as anode and in series with a suitable cathode.

3. Process of making beryllium, which com- 105 prises maintaining a fluid alloy of' beryllium and a metal or metals more dense than beryllium and lesselectropositive than beryllium in relation to fluorine, maintaning floating on at least a part of said alloy a fluid electrolyte containing a fluoride or fluorides selected from the alkali metal and alkaline earth metal uorides and containing a compound selected from the group consisting of beryllium fluoride and beryllium oxide, electrolyzing -the said electrolyte in series with said alloy as cathode and with a suitable anode, thereby d'ssociating said beryllium compound, liberating beryllium at the said cathode, and adding to the beryllium in said fluid alloy, maintaining oating on at least a part of the said fluid alloy an electrolyte 'containing a fluoride or fluorides selected from the alkali metal and alkaline earth metal'fluorides, and el'ectrolyzing said last mentioned electrolyte in series with said uid alloy as anode and in series with a suitable cathode, thereby depositing free beryllium at the saidl cathode. I f

4. Process of making beryllium, which comprises maintaining a fluid alloy of beryllium and a metal or vmetals relatively more dense than beryllium and -less electropositive -than beryllium in relationto fluorine, maintaining floating on a part of said alloy a fluidelectrolyte containing a metallic lfluoride or-iluorides of higher dissociation potential than beryllium fluoride and containing a compound selected from the group consisting of beryllium fluoride and beryllium oxide, electrolyzing said electrolyte in series with said alloy as cathode and with a suitable anode, thereby dissociating the said beryllium compound, liberating beryllium at `the said-cathode and adding to the beryllium in said uid alloy, maintaini-ng floating on a part o f the said fluid alloy a second fluid electrolyte containing a metallic fluoride or fluorides of higher dissociation potential than beryllium fluoride and containing a compound selected from the group consisting of beryllium fluoride and beryllium oxide, electrolyzingsaid second electrolyte in series with said uid alloy as anode and with a suitable cathode, 150

thereby depositing beryllium at the said last mentioned cathode.

5. Process of making beryllium, which comprises maintaining a fluid alloy consisting predominantly of beryllium and copper, maintaining floating on a part of said alloy a first fluid electrolyte containing a metallicuoride or fluorides of higher dissociation potential than beryllium iiuoride and containing a compound selected from the group consisting of beryllium chloride and beryllium oxide, electrolyzing the said electrolyte in series with saidA alloy as cathode and with a suitable anode, thereby dissociating the said beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in said alloy, maintain floating on a part ofthe said fluid alloy a second fluid electrolyte containing a metallic iluorideor fluorides of higher dissociation potential than beryllium fluoride and containing a compound 'selected from the group consisting of beryllium iiuoride and beryllium oxide, electrolyzing said second electrolyte .in series with said fluid alloy as anode and with a suitable cathode, thereby depos- -iting beryllium at the said last mentioned cathode.

6. Process of making beryllium, which comprises maintaining a fluid alloy of beryllium and a metal or metals more dense than beryllium and less electropositive than beryllium in relation to iiuorine, maintaining floating on a part of said alloy a iiuid electrolyte containing a iiuoride or fluorides selected from the alkali metal and a1- kaline earth metal fluorides and containing a compound selected from the group consisting o`f beryllium uoride and beryllium oxide, electrolyzing the said electrolyte in series with said alloy as cathode and with a suitable anode, thereby dissociating the said beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in said fluid alloy, maintaining oating on a part of the said iiuid alloy a second electrolyte containing a fluoride or uorides selected from the alkali metal and alkaline earth metal fluorides, and electrolyzing said last mentioned electrolyte in .series with said fluid alloy as anode and with a suitable cathode, thereby depositing free beryllium at the said cathode.

7. Process of making beryllium, which comprises maintaining a fluid alloy of beryllium and a metal or metals relatively more dense than beryllium and less electropositive'than beryllium in relation to uorine,` maintaining floating on said alloy a uid electrolyte containing a metallic fluoride' or uorides of higher dissociation potential than beryllium uoride and containing a compound selected from the group consisting of beryllium iiuoride and beryllium oxide, electrolyzing said electrolyte in series withv said alloy as cathode and with a suitable anode, thereby dissociating said beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in the said alloy, thereafter reversing the electrolysis, and electrolyzing the said electrolyte in series with said alloy as anode and with a suitable cathode, thereby depositing beryllium at the said last mentioned cathode.

8. Process of making beryllium, which comprises maintaining a fluid alloy consisting predominantly of beryl-lium and copper, maintaining floating on said iiuid alloy a fluid electrolyte convtaining a metallic fluoride or fluorides of higher dissociation potential than beryllium fluoride and containing a compound selected from the group consisting of beryllium fluoride and beryllium oxide, electrolyzing said electrolyte in series with said iiuid alloy as cathode and with a suitable anode, thereby dissociating said beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in said fluid alloy, thereafter reversing the electrolysis, and electrolyzing the said electrolyte in series with said iiuid alloy as anode and in series with a suitable cathode, thereby depositing free beryllium at the said cathode. y

9. Process of making beryllium, which comprises maintaining a fluid alloy of beryllium and a metal or metals more dense than beryllium and less electropositive than beryllium in relation to iiuorine, maintaining floating on said alloy a uid electrolyte containing a iiuoride or fluorides selected from the alkali metal and alkaline earth metal iiuorides and containing a compound selected from the group consisting of beryllium fluoride and beryllium* oxide, electrolyzing the said electrolyte in series with said alloy as cathode and with a suitable anode, thereby dissociating i said beryllium compound, liberating beryllium at the said cathode and adding to the beryllium in the said fluid alloy, thereby reversing the electrolysis, and electrolyzing the said electrolyte in series with said fluid alloy as anode and in series with a suitablercathode, thereby depositing free beryllium at the said cathode.

Louis BURGEss.

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